Biomass-derived methyl methacrylate and corresponding manufacturing method, uses and polymers

ABSTRACT

The invention relates to methyl methacrylate characterized in that at least one portion of the carbons thereof is biologically sourced and, more specifically, in that it contains between 0.2×10 −10  and 1.2×10 −10  wt.-% of  14 C in relation to total carbon weight according to the ASTM D6866 standard. The preparation method comprises the use of acetone cyanohydrin as a raw material, said acetone cyanohydrin being obtained by condensing cyanohydric acid on acetone, and the methyl methacrylate is prepared using a process involving the addition of methanol. According to the invention, at least one from among the acetone, cyanohydric acid and methanol is obtained by means of a reaction or series of reactions involving the biomass.

The present invention relates to a biomass-derived methyl methacrylate,to a method for the manufacture thereof, to the uses of this methylmethacrylate and to the polymers thereof.

Methyl methacrylate is the starting product for numerous polymerizationor copolymerization reactions.

It is the monomer for the manufacture of poly(methyl methacrylate)(PMMA), known under the trademarks Altuglas® and Plexiglas®. It existsin the form of powders, granules or sheets, the powders or granulesbeing used for molding various articles, such as articles for the carindustry, household articles and office articles, and sheets finding usein signs and displays, and in the transport, building, lighting andbathroom sectors, such as antinoise walls, for works of art, flatscreens, etc.

Methyl methacrylate is also the starting product for the organicsynthesis of higher methacrylates, which, like methyl methacrylate, areused in the preparation of acrylic emulsions and acrylic resins, serveas additives for poly(vinyl chloride), are used as comonomers in themanufacture of numerous copolymers such as methylmethacrylate-butadiene-styrene copolymers, serve as additives forlubricants, and have many other applications among which could bementioned medical prostheses, flocculants, cleaning products, etc.Acrylic emulsions and resins find applications in the paint, adhesive,paper, textile, ink, etc., sectors. Acrylic resins are also used in themanufacture of sheets, having the same applications as PMMA.

Methyl methacrylate can be obtained in various ways, the most commonroute being that with acetone cyanohydrin (Techniques de l'Ingénieur,Traité Génie des Precédés, J 6400 1-6).

In this method, acetone is reacted with hydrogen cyanide under basiccatalysis in order to form acetone cyanohydrin. The latter is reactedwith sulfuric acid, giving rise, through a highly exothermic reaction,to the formation of α-oxyisobutyramide monosulfate, which is convertedto sulfuric methacrylamide. The latter is then hydrolyzed and esterifiedwith methanol to form the desired methyl methacrylate, and also ammoniumhydrogen sulfate, the latter being recovered in order to regenerate thesulfuric acid.

Acetone is the coproduct of the synthesis of phenol obtained bydecomposition of cumene hydroperoxide. Hydrogen cyanide is obtainedeither as a by-product of the synthesis of acrylonitrile by ammoxidationof propylene, or by the reaction of methane or methanol with ammonia.Ammonia was obtained by the reaction of nitrogen and hydrogen, thelatter being itself generally obtained by steam reforming of methaneand/or by water gas shift of the synthesis gas.

The starting materials used for the synthesis of methyl methacrylate aremainly of petroleum origin or of synthetic origin. This method thuscomprises numerous sources of CO₂ emissions, which have been reported inthe literature as being 5600 g/kg of PMMA (Catalysis Today 99, 2005,5-14) and consequently contribute to the increase in the greenhouseeffect. Given the decrease in world petroleum reserves, the source ofthese starting materials will gradually run out.

Biomass-derived starting materials are from a renewable source and havea smaller impact on the environment. They do not require all therefining steps, which are very expensive in terms of energy, ofpetroleum products. The production of CO₂ is reduced such that theycontribute less to global warming. The plant consumed, especially forits growth, atmospheric CO₂ in an amount of 44 g of CO₂ per mole ofcarbon (or per 12 g of carbon). The use of a renewable source thereforebegins by reducing the amount of atmospheric CO₂. Plant materials havethe advantage that they can be cultivated in large amounts, according todemand, on most of the planet Earth, including by algae and microalgaein the marine environment.

It therefore appears to be necessary to have methods for synthesizingmethyl methacrylate which are not dependent on a starting material offossil origin, but which instead use biomass as starting material.

The term “biomass” is intended to mean starting material of plant oranimal origin that is produced naturally. This plant material ischaracterized in that the plant has consumed atmospheric CO₂ for itsgrowth, while producing oxygen. Animals, for their part, have consumedthis plant starting material for their growth and have therebyassimilated the carbon derived from atmospheric CO₂.

The objective of the present invention is therefore to respond tocertain concerns of sustainable development and to provide a methylmethacrylate in which at least a portion of the carbons thereof is ofrenewable origin, or biobased.

A renewable or biobased starting material is an animal or plant naturalresource of which the stock can be reconstituted over a short period oftime on the human scale. It is in particular necessary for this stock tobe renewed as quickly as it is consumed.

Unlike materials derived from fossil materials, biobased staringmaterials contain ¹⁴C in the same proportions as atmospheric CO₂. Allthe carbon samples taken from living organisms (animals or plants) arein fact a mixture of 3 isotopes: ¹²C (representing approximately98.892%), ¹³C (approximately 1.108%) and ¹⁴C (traces: 1.2×10⁻¹⁰%). The¹⁴C/¹²C ratio of living tissues is identical to that of the atmosphere.In the environment, ¹⁴C exists in two predominant forms: in inorganicform, i.e. in the form of carbon dioxide (CO₂), and in organic form,i.e. in the form of carbon incorporated into organic molecules.

In a living organism, the ¹⁴C/¹²C ratio is kept constant by themetabolism because carbon is continually exchanged with the environment.Since the proportion of ¹⁴C is constant in the atmosphere, the same istrue in the organism, as long as it is alive, since it absorbs this ¹⁴Cin the same way that it absorbs ¹²C. The mean ¹⁴C/¹²C ratio is equal to1.2×10⁻¹² for a biobased material, whereas a fossil starting material(for example derived from petroleum, from natural gas or from coal) hasa zero ratio.

Carbon 14 is derived from the bombardment of atmospheric nitrogen (14),and is spontaneously oxidized with atmospheric oxygen to give CO₂. Inour human history, the ¹⁴CO₂ content has increased following atmosphericnuclear explosions, and then has not stopped decreasing now that thesetests have been stopped.

¹²C is stable, i.e. the number of ¹²C atoms in a given sample isconstant over time. ¹⁴C is, itself, radioactive (each gram of carbon ofa living being contains a sufficient amount of ¹⁴C isotopes to give 13.6disintegrations per minute) and the number of such atoms in a sampledecreases over time (t) according to the law:

n=no exp(−at),

in which;

-   -   no is the number of ¹⁴C atoms at the start (on the death of the        animal or plant creature),    -   n is the number of ¹⁴C atoms remaining at the end of the time t,    -   a is the disintegration constant (or radioactive constant); it        is linked to the half-life.

The half-life (or period) is the period after which any number ofradioactive nuclei or of unstable particles of a given entity is reducedby half by disintegration; the half-life T_(1/2) is linked to thedisintegration constant a by the formula a T_(1/2)=ln 2. The half-lifeof ¹⁴C is 5730 years. Within 50 000 years, the ¹⁴C content is less than0.2% of the initial content and therefore becomes difficult to detect.Petroleum products, or natural gases or coal do not therefore contain¹⁴C.

Given the half-life (T_(1/2)) of ¹⁴C, the ¹⁴C content is substantiallyconstant from the extraction of the biobased starting materials to themanufacture of the methyl methacrylate according to the invention andeven to the end of its use.

The ¹⁴C content of a “biomaterial” can be deduced for measurementscarried out, for example, according to the following techniques:

-   -   by liquid scintillation spectrometry: this method consists in        counting “Beta” particles derived from the disintegration of        ¹⁴C. The Beta-radiation derived from a sample of known mass        (known number of carbon atoms) is measured for a certain period        of time. This “radioactivity” is proportional to the number of        ¹⁴C atoms, which can thus be determined. The ¹⁴C present in the        sample emits β-radiation which, on contact with the        scintillation fluid (scintillator), gives rise to photons. These        photons have different energies (between 0 and 156 Key) and form        what is known as a ¹⁴C spectrum. According to two variants of        this method, the analysis relates either to the CO₂ previously        produced by combustion of the carbon sample in an appropriate        absorbent solution, or to benzene after prior conversion of the        carbon sample to benzene;    -   by mass spectrometry: the sample is reduced to graphite or to        CO₂ gas, and analyzed in a mass spectrometer. This technique        uses an accelerator and a mass spectrometer to separate the ¹⁴C        ions from the ¹²C ions and therefore to determine the ratio of        the two isotopes.

These methods of measuring the ¹⁴C content of materials are describedprecisely in standards ASTM D 6866 (in particular D6866-06) and instandards ASTM D 7026 (in particular 7026-04). These methods compare thedata measured on the analyzed sample with the data for a referencesample which is of 100% biobased origin, so as to give a relativepercentage of biobased carbon in the sample. The ¹⁴C/¹²C ratio or thecontent by mass of ¹⁴C relative to the total mass of carbon, can then bededuced therefrom for the sample analyzed.

The method of measurement preferably used is the mass spectrometrydescribed in standard ASTM D6866-06 (“accelerator mass spectroscopy”).

The methyl methacrylate of the present invention contains organic carbonoriginating from biomass, determined according to standard ASTM D6866.

The subject of the present invention is therefore firstly a methylmethacrylate characterized in that it contains from 0.2×10⁻¹⁰% to1.2×10⁻¹⁰% by mass of ¹⁴C relative to the total mass of carbon accordingto standard ASTM D6866, preferably from 0.4×10⁻¹⁰% to 1.2×10⁻¹⁰% by massof ¹⁴C, more particularly from 0.6×10⁻¹⁰% to 1.2×10⁻¹⁰% by mass of ¹⁴C,even more preferably from 0.8×10⁻¹⁰% to 1.2×10⁻¹⁰% by mass of ¹⁴C.

In one preferred embodiment of the invention, the methyl methacrylateaccording to the invention contains 100% of organic carbon derived frombiobased starting materials and, consequently, 1.2×10⁻¹⁰% by mass of ¹⁴Crelative to the total mass of carbon.

The subject of the present invention is also a composition of monomerscontaining methyl methacrylate as defined above and at least onepolymerizable comonomer. The polymerizable comonomer(s) is (are) inparticular chosen from vinyl, vinylidene, diene and olefin monomers.

The term “vinyl monomers” is intended to mean acrylic acid or its saltsof alkali or alkaline-earth metals, such as sodium, potassium orcalcium, (meth)acrylates, vinylaromatic monomers, vinyl esters,(meth)acrylonitrile, (meth)acrylamide and mono- and di-(alkyl containing1 to 22 carbon atoms)-(meth)acrylamides, and monoesters and diesters ofmaleic anhydride or acid.

The (meth)acrylates are in particular those of formulae, respectively:

CH₂═C(CH₃)—COOR⁰ and CH₂═CH—COO—R¹

in which R⁰ and R¹ are chosen from the following radicals: alkylcomprising from 1 to 22 primary, secondary or tertiary, linear orbranched carbon atoms, cycloalkyl comprising from 5 to 18 carbon atoms,(alkoxy containing 1 to 18 carbon atoms)-(alkyl containing 1 to 22carbon atoms), (alkylthio containing 1 to 18 carbon atoms)-(alkylenecontaining 1 to 18 carbon atoms), aryl and arylalkyl, these radicalsbeing optionally substituted with at least one halogen atom (such asfluorine) and/or at least one hydroxyl group after protection of thishydroxyl group, the above alkyl groups being linear or branched, itbeing possible for R¹ to also represent a methyl; and glycidyl,norbonyl, naphthyl and isobornyl (meth)acrylates.

As examples of methacrylates, mention may be made of ethyl,2,2,2-trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, n-amyl, i-amyl, n-hexyl, 2-ethylhexyl, cyclohexyl, octyl,i-octyl, nonyl, decyl, lauryl, stearyl, phenyl, benzyl, β-hydroxyethyl,isobornyl, hydroxypropyl and hydroxybutyl methacrylates.

As examples of acrylates of the above formula, mention may be made ofmethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,hexyl, 2-ethylhexyl, isooctyl, 3,3,5-trimethylhexyl, nonyl, isodecyl,lauryl, octadecyl, cyclohexyl, phenyl, methoxymethyl, methoxyethyl,ethoxymethyl, ethoxyethyl and perfluorooctyl acrylates.

For the purpose of the present invention, the term “vinylaromaticmonomer” is intended to mean an ethylenically unsaturated aromaticmonomer such as styrene, vinyltoluene, alpha-methylstyrene,4-methylstyrene, 3-methyl styrene, 4-methoxystyrene,2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene,3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene,4-chloro-3-methylstyrene, 3-tert-butylstyrene, 2,4-dichlorostyrene,2,6-dichlorostyrene and 1-vinylnaphthalene.

As vinyl esters, mention may be made of vinyl acetate, vinyl propionate,vinyl chloride, chlorinated vinyl chloride and vinyl fluoride.

As vinylidene monomer, mention may be made of vinylidene fluoride.

The term “diene monomer” is intended to mean a diene chosen fromconjugated or non-conjugated, linear or cyclic dienes such as, forexample, butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene,1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene,5-methylene-2-norbornene, 5-vinyl-2-norbornene,2-alkyl-2,5-norbornadienes, 5-ethylene-2-norbornene,5-(2-propenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene,1,5-cyclooctadiene, bicyclo[2,2,2]octa-2,5-diene, cyclopentadiene,4,7,8,9-tetrahydroindene and isopropylidene tetrahydroindene.

As olefin monomers, mention may be made of ethylene, butene, hexene and1-octene. The fluorinated olefin monomers may also be mentioned.

Also forming the subject of the present invention are: a homopolymerresulting from the polymerization of methyl methacrylate as definedabove, and also a copolymer obtained from a composition of monomers asdefined above.

The term “copolymer” is intended to mean the copolymers obtained bypolymerization of two monomers and the polymers formed from threemonomers or more, such as terpolymers. The term “polymer” is intended tomean homopolymers and copolymers.

The polymers are prepared by free-radical polymerization according totechniques known to those skilled in the art. The polymerization can becarried out in the solution, in the mass, in an emulsion or in asuspension. The polymers may also be prepared by anionic polymerization.

The copolymer according to the invention may have a random, block oralternating structure.

In particular, also forming the subject of the invention is a blockcopolymer in which one of the blocks results from the polymerization ofmethyl methacrylate as defined above.

As examples of block copolymers, mention may be made of methylmethacrylate-styrene copolymers; methyl methacrylate-butadiene-styrenecopolymers; styrene-butadiene-methyl methacrylate copolymers; and methylmethacrylate-butyl acrylate-methyl methacrylate copolymers.

The copolymer according to the invention may also have a core-shellstructure. The term “core-shell structure” is intended to mean amultilayer structure having at least one elastomeric (or soft) layer,i.e. a layer formed from a polymer having a T_(g) of less than −5° C.,and at least one rigid (or hard) layer, i.e. formed from a polymerhaving a T_(g) greater than 25° C.

Preferably, the polymer having a T_(g) of less than −5° C. is obtainedfrom a mixture of monomers comprising from 50 to 100 parts of at leastone C₁-C₁₀ alkyl (meth)acrylate, from 0 to 50 parts of a copolymerizablemonounsaturated comonomer, from 0 to 5 parts of a copolymerizablecrosslinking monomer and from 0 to 5 parts of a copolymerizable graftingmonomer. The C₁-C₁₀ alkyl (meth)acrylate is preferably butyl acrylate,2-ethylhexyl acrylate or octyl acrylate.

Preferably, the polymer having a T_(g) greater than 25° C. is obtainedfrom a mixture of monomers comprising from 70 to 100 parts of methylmethacrylate, from 0 to 30 parts of a copolymerizable monounsaturatedmonomer, from 0 to 5 parts of a copolymerizable crosslinking monomer andfrom 0 to 5 parts of a copolymerizable grafting monomer. Preferably, thepolymer having a T_(g) greater than 25° C. has a weight-averagemolecular mass, expressed in PMMA equivalents, of between 10 000 and 1000 000, advantageously between 50 000 and 500 000 g/mol.

The copolymerizable monounsaturated monomer may be a C₁-C₁₀ alkyl(meth)acrylate, styrene, alpha-methylstyrene, butylstyrene oracrylonitrile. It is preferably styrene or ethyl acrylate. The graftingmonomer may be allyl (meth)acrylate, diallyl maleate or crotyl(meth)acrylate.

The crosslinking monomer may be diethylene glycol dimethacrylate,1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate,divinylbenzene or trimethylolpropane triacrylate (TMPTA).

In one particular embodiment of the invention, the methyl methacrylatehomopolymer as defined above and/or the copolymer obtained from acomposition of monomers as defined above are impact-strengthened bymeans of at least one impact modifier.

The impact modifier may be an acrylic elastomer such as the blockcopolymers methyl (meth)acrylate-styrene; butyl (meth)acrylate-styrene;styrene-butadiene-methyl (meth)acrylate; methyl (meth)acrylate-butylacrylate-methyl (meth)acrylate, etc.

The impact modifier may also be in the form of fine multilayer particleshaving a core-shell structure as defined above. The multilayer particlesmay be of various morphologies. It is possible to use, for example,particles of the “soft-hard” type having an elastomeric nucleus (innerlayer) and a rigid shell (outer layer). European application EP 1061100A1 describes such particles. It is also possible to use particles of the“hard-soft-hard” type having a rigid nucleus, an elastomericintermediate layer and a rigid shell. Application US 2004/0030046 A1describes examples of such particles. It is also possible to useparticles of the “soft-hard-soft-hard” type having, in order, anelastomeric nucleus, a rigid intermediate layer, another elastomeric,intermediate layer and a rigid shell. French application FR-A-2446296describes examples of such particles.

The present invention therefore also relates to a polymer compositioncontaining at least one polymer as defined above, in particular acomposition comprising:

a matrix polymer comprising at least one methyl methacrylate homopolymeras defined above and/or at least one copolymer as defined above; anda polymer additive, such as an impact modifier, chosen in particularfrom block copolymers, in particular as defined above, such as the blockcopolymers methyl (meth)acrylate-styrene; butyl (meth)acrylate-styrene;styrene-butadiene-methyl (meth)acrylate; methyl (meth)acrylate-butylacrylate-methyl (meth)acrylate; etc., and polymers of the “core-shell”type, in particular as defined above.

The polymer composition may also comprise at least one additive chosenfrom thermal stabilizers, for example tert-dodecyl disulfide (DtDDS) orIrganox© 1076; lubricants; for example stearic acid or stearyl alcohol;flame retardants, for example antimony trioxide or a brominated orchlorinated phosphate ester; organic or inorganic pigments; anti-UVagents, for example Tinuvin© P; antioxidants, such as hindered phenoliccompounds; antistatic agents; inorganic fillers, such as, for example,tale, calcium carbonate, titanium dioxide or zinc oxide, or organicfillers.

The polymer composition according to the invention may be in the form ofa powder, of granules or of pellets.

The polymer composition according to the invention is in particular usedfor the manufacture of items and articles of everyday life. They may be,for example, boxes or casings for mowers, chainsaws, jet skis, domesticappliances, car roof boxes; car body parts; license plates; externalwall panels for caravans and for mobile homes; external panels forrefrigerators; panels for shower cubicles; doors of buildings; windowmoldings; cladding panels.

The present invention also relates to the use of a homopolymer asdefined above, of a copolymer as defined above or of a polymercomposition as defined above, for the manufacture of sheets, castsheets, films, layers, fibers and tubes.

The subject of the present invention is also:

-   -   a multilayer structure comprising at least one layer obtained        from a homopolymer, from at least one copolymer or from at least        one polymer composition as defined above;    -   an extrudable resin comprising a polymer matrix based on a        homopolymer as defined above and/or on at least one copolymer as        defined above and highly crosslinked polymer particles such as        those described, for example, in patent EP 1022115;    -   an acrylic emulsion or an acrylic resin, incorporating a        homopolymer and/or at least one copolymer as defined above;    -   a manufactured article obtained from at least one composition as        defined above, such as articles for the car industry, household        articles and office articles, signs and displays, articles in        the transport, building, lighting and bathroom sectors;    -   an article obtained by extrusion, coextrusion, hot pressing or        multi-injection molding using at least one composition as        defined above.

The subject of the present invention is also a method for themanufacture of a starting material containing mainly methyl methacrylateas defined above, according to which acetone cyanohydrin obtained bycondensation of hydrocyanic acid with acetone is used as reactant, andmethyl methacrylate is prepared by a route involving the introduction ofmethanol, characterized in that at least one from among acetone,hydrocyanic acid and methanol was obtained by a reaction or a successionof reactions starting from biomass.

The method according to the invention may also comprise one or morepurification steps.

The expression “starting material containing mainly methyl methacrylate”means that the method results in the production of methyl methacrylateMMA possibly comprising impurities linked to the nature of the reactantsused, or generated during the method, it being possible for this methylmethacrylate to then be used, optionally after a purification step, asstarting material in all the applications in which it is known practiceto use MMA, in particular for the uses described above, in particularfor preparing monomer compositions containing MMA, an MMA homopolymer orMMA-based copolymers, or else MMA-based polymer compositions up to theobtaining of the manufactured articles described above.

A reaction scheme for manufacture of methyl methacrylate is thefollowing:

Exploiting the Potential of Biomass as Acetone

In accordance with a first embodiment, the acetone was obtained byacetobutylic fermentation of C₆ and C₅ sugars, resulting in anacetone-butanol mixture, where appropriate with ethanol, from which theacetone was separated, for example, by distillation, in particularazeotropic distillation, or by membrane separation (for example onpervaporation membranes) or separation on silicalite (Revue del'Institut Français du Pétrole [French Petroleum Institute Review], vol.36, No. 3, 1981, pp. 339-347; Biotechnology Letters, vol. 4, No. 11, pp.759-760 (1982); Advances in Applied Microbiology, volume 31, 1986, pp.61-92; Prog. Ind. Microbiol 3(190) 73-90; Separation, Science andTechnology ([28 (13 & 14), pp. 2167-2178, 1993]; Biotechnology Letters,vol. 4, No. 11, 759-760 (1982)).

The C₆ and C₅ sugars were advantageously obtained from a material with ahigh sugar content, chosen in particular from agriculturallignocellulosic residues and any materials of plant origin, such ascereal straw fodder, for instance wheat straw, corn straw or corn earresidues; cereal residues, for instance corn residues; cereal flours,for instance wheat flour; cereals such as wheat, barley, sorghum, corn;wood, wood waste and scraps; grains; sugarcane; sugarcane residues; peatwinings and stems; beet, molasses such as beet molasses; Jerusalemartichokes; potatoes, potato haulms, potato residues; starch; mixturesof cellulose, hemicellulose and lignin; which have been subjected, whereappropriate, to a mechanical treatment, such as shredding, grinding orextrusion, and/or to a chemical treatment, such as acid or base steamtreatment, and/or to an enzyme hydrolysis treatment in order to releasethe C₆ and C₅ sugars.

The mechanical and chemical pretreatments are intended to reduce thecrystallinity of cellulose by breaking bonds and to increase the surfacearea of contact between cellulose and enzymes.

The hydrolysis step allows in particular the saccharification of starchin order to convert it to glucose or to convert sucrose to glucose.

In particular, an acetobutylic fermentation has been carried out withanaerobic bacteria such as Clostridium beijerinckii, such as VPI 5481(ATCC 25732), 4635, 2697, 4419 (ATCC 11914), Clostridium butylicum, suchas VPI 13436 (NRRLB-592), Clostridium aurantibutyricum, such as VPI 4633(ATCC 17777), 10789 (NCIB 10659), Clostridium acetobutylicum, such asVPI 2673 (McClung 633), 13697 (ATCC 4259), 13698 (NRRL B—527—ATCC 824),13693 (ATCC 8529), 2676 (McClung 635), Clostridium toanum, the mutantsor genetically modified organisms thereof (Applied and EnvironmentalMicrobiology, March 1983, pp. 1160-1163, vol. 45, No. 3; BiotechnologyLetters, vol. 4, No. 8 (1982) 477-482).

These fermentation methods are known to those skilled in the art who areable to choose the best working conditions for a given type of plantmaterial (Microbiological Reviews, December 1986, vol. 50, No. 4, pp.484-524; Bioresource Technology 42 (1992) 205-217; Appl MicrobiolBiotechnol (1985) 23: 92-98; Energy from Biomass, W. Palz, Elsevier,Applied Science, London (1985), pp. 692-696).

In accordance with a second embodiment, the acetone was obtained byhydrothermal liquefaction at 573 K of sewage treatment sludge in orderto obtain black water containing hydrocarbons, followed by catalyticcracking of said black water in a steam atmosphere on a catalyst basedon zirconia or zirconia/alumina supported on iron oxide, and thenseparation of the acetone as indicated above, namely, for example, bydistillation, in particular azeotropic distillation, or by membraneseparation or separation on silicalite (Applied Catalysis B:Environmental 68 (2006) 154-159).

In accordance with a third embodiment, the acetone was obtained bycatalytic conversion of palm oil residues on a catalyst based onzirconia or zirconia/alumina supported on iron oxide and then separationof the acetone as indicated above, namely, for example, by distillation,in particular azeotropic distillation, or by membrane separation orseparation on silicalite (Applied Catalysis B: Environmental 68 (2006)154-159).

Exploiting the Potential of Biomass as Hydrocyanic Acid and as Methanol(a) as Hydrocyanic Acid

In accordance with a first embodiment, the hydrocyanic acid was obtainedby ammoxidation of methane, the methane having been obtained byfermentation, in particular in the absence of oxygen, of animal and/orplant organic materials, such as pig manure, household refuse, foodindustry waste, resulting in a biogas mainly composed of methane andcarbon dioxide, the carbon dioxide having been removed by washing thebiogas with a basic aqueous solution of sodium hydroxide, potassiumhydroxide or amine, or else with water under pressure, or by absorptionin a solvent such as methanol.

This fermentation, also called methanization, occurs naturally orspontaneously in garbage dumps containing organic waste, but can also becarried out in digesters, in order to treat, for example, sewagetreatment sludge, industrial or agricultural organic waste, pig manureand household refuse.

Preferably, the fermented mixture contains animal feces, which serve asnitrogen input necessary for the growth of the microorganisms fermentingthe biomass to give methane. Reference may be made to the variousmethanization technologies of the prior art, to the article “Review ofCurrent Status of Anaerobic Digestion Technology for Treatment ofMunicipal Solid Waste”, November 1998, RISE-AT, and to the variousbiological methods that exist for the treatment of wastewater, forinstance the Linde Laran® process.

Mention may be made of an ammoxidation of methane according to whichammonia (where appropriate obtained from biomass) is reacted withmethane in the presence of air and, optionally, of oxygen on a catalystcomposed of rhodium-containing platinum gauze at a temperature rangingfrom 1050 to 1150° C. Generally, the CH₄NH₃ molar ratio ranges from 1.0to 1.2, the (CH₄+NH₃)/total O₂ molar ratio ranges from 1.6 to 1.9; thepressure is generally from 1 to 2 bar.

In accordance with a second embodiment, the hydrocyanic acid wasobtained by ammoxidation of methanol, the methanol having been obtainedby pyrolysis of wood or by gasification of any materials of animal orplant origin, resulting in a syngas essentially composed of carbonmonoxide and of hydrogen, which is reacted with water, or byfermentation starting from plant crops such as wheat, sugarcane or beet,giving fermentable products and therefore alcohol.

The materials of animal origin are, by way of nonlimiting examples, fishoils and fats, such as cod liver oil, whale oil, sperm whale oil,dolphin oil, seal oil, sardine oil, herring oil and shark oil, bovine,porcine, caprine, equine and poultry oils and fats, such as tallow,lard, milk fat, baking fat, chicken, cow, pig and horse fat, and thelike.

The materials of plant origin are those described above as startingmaterials for acetobutylic fermentation. Papermill black liquor, whichis a carbon-rich starting material, will be added thereto.

The method for the manufacture of HCN by ammoxidation of methanol:

CH₃OH+NH₃+O₂→HCN+3H₂O

was described in particular in the 1950s-1960s in patents GB 718,112 andGB 913,836 by Distillers Company. It uses a catalyst based on molybdenumoxide at a temperature ranging from 340° C. to 450° C., or a catalystbased on antimony and tin at a temperature ranging from 350° C. to 600°C. Reference may be made to the article by Walter Sedriks in ProcessEconomics Reviews PEP'76-3, June 1977. This method has been the subjectof various improvements, in particular in terms of the catalytic systemsused; mention may, for example, be made of systems based on mixedmolybdenum-bismuth-iron oxides supported on silica (U.S. Pat. No.3,911,089 by Sumitomo, U.S. Pat. No. 4,511,548 by The Standard OilCompany, JP 2002-097017 by Mitsubishi), the catalysts based on Fe—Sb—Odescribed by Nitto Chemical Industry (EP 340 909, EP 404 529, EP 476579, Science and Technology in Catalysis 1998, pages 335-338, AppliedCatalysis A: General 194-195, 2000, 497-505) or by Mitsubishi (JP2002-097015, JP 2002-097016, EP 832 877).

(b) as Methanol

In accordance with one particular embodiment of the present invention,the methanol was obtained as starting material in the manufacture of themethyl methacrylate of the invention, by pyrolysis of wood, bygasification or by fermentation according to what has just beendescribed above for the production of hydrocyanic acid by ammoxidationof methanol.

According to one particular embodiment of the invention, the syngas forpreparing methanol is obtained from the recovery of residual liquor fromthe manufacture of cellulosic pulps. Reference may be made to documentsEP 666 831 and U.S. Pat. No. 7,294,225 by Chemrec, which describe inparticular the gasification of residual liquors from the manufacture andbleaching of cellulose, and the production of methanol, and also topages 92-105 of the book Procédés de pétrochimie—Caractéristiquestechniques et économiques [Petrochemical Processes—technical andeconomical characteristics] —volume 1—Technip Editions—le gaz desynthèse et ses dérivés [syngas and derivatives thereof], whichdiscusses the production of methanol from syngas.

The methanol used in the ammoxidation of methanol above canadvantageously be biomass-derived.

Manufacture of the Starting Material Containing Mainly MethylMethacrylate

In accordance with a first embodiment:

-   -   in a first step, hydrocyanic acid is condensed with acetone via        a basic catalysis in order to obtain acetone cyanohydrin;    -   in a second step, the acetone cyanohydrin is reacted in a        concentrated sulfuric medium in order to obtain        α-oxyisobutyramide monosulfate, which is converted to sulfuric        methacrylamide under the action of the heat of the reaction        which is highly exothermic;    -   in a third step, the methacrylamide is hydrolyzed and esterified        with methanol so as to form methyl methacrylate and ammonium        hydrogen sulfate, and the desired starting material is        recovered.

In accordance with a second embodiment:

-   -   in a first step, hydrocyanic acid is condensed with acetone via        a basic catalysis in order to obtain acetone cyanohydrin;    -   in a second step, the acetone cyanohydrin is reacted with        methanol in order to obtain methyl hydroxymethacrylate;    -   in a third step, the methyl hydroxymethacrylate is dehydrated so        as to recover the desired starting material.

The invention also relates to the starting material containing mainlymethyl methacrylate having from 0.2×10⁻¹⁰% to 1.2×10⁻¹⁰% by mass of ¹⁴Crelative to the total mass of carbon according to standard ASTM D6866,obtained according to the method as described above.

The following examples illustrate the present invention without,however, limiting the scope thereof. In these examples, the parts andpercentages are by weight unless otherwise indicated.

EXAMPLE 1 Manufacture of Acetone from Wheat Straw by Enzyme HydrolysisFollowed by Acetobutylic Fermentation

The procedure is carried out as described in the Revue de l'InstitutFrançais de Pétrole [French Petroleum Institute Review], vol. 36, No. 3,May-June 1981, pages 339-347.

The wheat straw is shredded in a shredder and then the shredded straw isground in a hammermill. This is followed by treatment with acid at a lowconcentration at a temperature of 100° C. for approximately 1 hour.

After neutralizing the acid, the medium is brought to a pH in the regionof 5, which is required for enzyme hydrolysis.

A cellulose solution is prepared in the presence of nutritive elementsin fermenters in series, the culturing of the microorganism Trichodermareesi being carried out in the first fermenters starting from previouslyground straw, and cellulose being produced in the subsequent fermenters.The desired enzyme solution is separated from the content of the finalfermenter by centrifugation and filtration.

Enzyme hydrolysis of the above pretreated straw is carried out with theabove enzyme solution in reactors mounted in series.

After filtration, C₆ and C₅ sugar solutions are recovered. The filtratewhich contains lignin is dried so as to serve as fuel.

An acetobutylic fermentation is carried out on the above C₆ and C₅ sugarsolutions using the microorganism Clostridium acetobutylicum underaseptic conditions.

The fermentation comprises two successive phases, the first resulting inthe production of acetic acid and butylic acid, and the second resultingin the production of acetone, butanol and ethanol in the followingproportions by weight: 68% butanol; 29% acetone; and 3% ethanol.

The acetone is separated by azeotropic distillation.

EXAMPLE 2 Synthesis of Acetone Cyanohydrin (AC)

For this batch synthesis, a 1-liter jacketed glass reactor is used,which is equipped with mechanical stirring and surmounted by acondenser. The temperature is controlled via a circulation of coldglycol-containing water in the jacket (cryostat).

69.5 g of pure HCN and 149.4 g of acetone previously obtained byfermentation according to example 1 (equimolar mixture) are introducedinto the previously cooled reactor (approximately 0° C.). As soon as themixture reaches the temperature of 0° C., 34 mg of diethylamine (DEA)catalyst are added. The temperature passes through a maximum of 18° C.within about 6 minutes and then stabilizes rapidly at around 0° C.Samples are taken manually (approximately 1 g) over time in order tomonitor the amount of unreacted HCN. The free HCN is assayed accordingto the Charpentier-Volhard method based on the precipitation of cyanideCN⁻ ions, by means of an excess of N/10 silver nitrate solution andtitration of the excess silver nitrate with an N/10 KSCN solution in thepresence of an Fe(SO₄)₃ indicator in solution. After reaction for 150minutes, a mixture comprising 1.53% by weight of free HCN, i.e. 0.533mol/l, is obtained, which is equivalent to 10.855 mol/l of HCN convertedand a degree of conversion to acetone cyanohydrin of 95.32 mol %.

The crude product is neutralized by adding excess sulfuric acid(neutralization of the basic catalyst) and then purified by vacuumdistillation. The unconverted HCN and acetone are removed at the top(gradual vacuum from 760 to 30 mmHg and maximum temperature ofapproximately 100° C.).

EXAMPLE 3 Synthesis of Acetone Cyanohydrin (AC)

The preceding example is reproduced with 69.5 g of HCN resulting fromthe ammoxidation of methane originating from biogas and 149.4 g ofacetone previously obtained by fermentation according to example 1. Thetarget reaction temperature is −15° C. (an exothermic peak at −9° C. isobserved for 9 minutes of reaction). The free HCN is monitored as in thepreceding example. After reaction for 340 minutes, a mixture is obtainedwhich comprises 1.20% by weight of free HCN, i.e. 0.418 mol/l, which isequivalent to 10.667 mol/l of HCN converted and a degree of conversionto acetone cyanohydrin of 96.23 mol %. After distillation of thereaction product according to the preceding example, acetone cyanohydrinpurified to 99.0-99.5% by weight is obtained.

EXAMPLE 4 Synthesis of Sulfuric Methyacrylamide (MACRYD)

Pure acetone cyanohydrin (AC) prepared according to the precedingexamples (titer 99.06% by weight) and 100% sulfuric acid (H₂SO₄)containing approximately 400 ppm of phenothiazine (polymerizationinhibitor) are used for the preparation of sulfuric methacrylamide.

The acetone cyanohydrin amidation reaction is carried out in amicropilot unit. The micropilot unit is composed of:

-   -   a stirred jacketed glass mixing reactor R1, itself composed of 3        stages each having a volume of 120 ml, and cooled with        thermostated water; each stage is separated by a perforated        diaphragm and stirred with a mixing turbine;    -   a piston flow jacketed glass precooking exchanger R1-2 having a        volume of 60 ml and heated with oil;    -   a second stirred jacketed glass mixing reactor R2 composed of 3        stages having a volume of 120 ml, i.e. a total of 360 ml, and        cooled with thermostatic water; each stage is separated by a        perforated diaphragm and stirred with a mixing turbine;    -   a piston flow jacketed glass cooking exchanger R3 having a        volume of 36 ml; and    -   a final baffled piston flow jacketed glass cooking reactor R4        having a total volume of 240 ml and heated with oil.

This cascade of reactors operates continuously. The reactants areinjected using pumps. The acetone cyanohydrin is introduced continuouslyinto each of the stages of the reactors R1 and R2, i.e. six points ofintroduction. The sulfuric acid is introduced continuously at the baseof the reactor R1. The reaction temperatures in R1, in R1-2, in R2, inR3 and in R4 are, respectively: 85° C., 120° C., 90° C., 140° C. and140° C. Only the residence time in the reactor R4 is critical. Therelative proportion of acetone cyanohydrin injected into R1 and R2 is70/30, with an equal distribution in each stage of the reactors.

Two series of synthesis are carried out:

-   -   H₂SO₄/AC molar ratio (MR)=1.30        -   total flow rate of AC: 426.33 g/h;        -   flow rate of H₂SO₄: 632.98 g/h.    -   H₂SO₄/AC molar ratio (MR)=1.25        -   total flow rate of AC: 433.54 g/h;        -   flow rate of H₂SO₄: 618.93 g/h.

After approximately three hours of normal operation, samples are takenfrom each stage of reaction for analyses.

The percentages, by mass, of methacrylamide and methacrylic acid aredetermined by HPLC analyses after diluting the samples in a phosphatebuffer medium.

The yield of (sulfuric methacrylamide+methacrylic acid) is determined atthe outlet of the reactor R4 on the basis of these analyses and relativeto the inflowing AC:

-   -   MR 1.30: yield 91.5 mol %;    -   MR 1.25: yield 90.8 mol %.

The waste (not quantified) consists mainly of carbon monoxide.

The sulfuric methacrylamide obtained is used as it is for the synthesisof methyl methacrylate.

EXAMPLE 5 Synthesis of Methyl Methacrylate (MMA)

The reaction for esterification of sulfuric methacrylamide with methanolis also carried out in a micropilot unit in continuous mode. Methanoloriginating from the reaction of a syngas obtained by gasification ofblack liquor is used. This second micropilot unit is composed of a10-stage glass plate reactive column into which the sulfuricmethacrylamide and a water-methanol mixture are injectedcountercurrentwise (reactive distillation).

-   -   At the top, the reactive column is surmounted by a distillation        column filled with multiknit packing and by its condenser. It        makes it possible to obtain crude methyl methacrylate.    -   At the base, a distiller makes it possible to collect “residual        liquor”, a mixture of ammonium hydrogen sulfate, sulfuric acid        and water. This “residual liquor” is stripped with steam so as        to recover the maximum amount of volatile organic compounds. A        guard tube makes it possible to maintain a level of liquid in        the distiller.

The sulfuric methacrylamide obtained in the preceding example (molarratio 1.25, temperature approximately 130° C.) is introduced at the topof the column at a flow rate of 838.9 g/h (i.e. as AC equivalent 344g/h). A methanol-water mixture (90-10% by weight) is introduced at twolevels of the reactive column: at the base with a flow rate of 155.2g/h, and at an intermediate point with a flow rate of 38.8 g/h(methanol/AC molar ratio: 1.35). The distiller is continuously strippedwith live steam at a flow rate of 275.1 g/h (steam/AC molar ratio: 3.78and total water/AC molar ratio: 4.05).

A methanolic solution of stabilizers containing phenothiazine isintroduced at the top of the reflux column (flow rate approximately 5g/h).

Using a timer, a crude methyl methacrylate reflux of 0.8 is maintainedin the reactive column.

Once the equilibrium has been reached (approximately 3 hours), theoperating conditions are the following:

-   -   distiller temperature: 125-130° C.;    -   reactor temperature: 110-115° C.;    -   reflux temperature: 87° C.

At the outlet, 3 streams are recovered: the waste at the top of thecondenser, the crude MMA at the top of the distillation column, and the“residual liquor” at the outlet of the distiller. The respective flowrates are the following: 5.4 l/h, 502.4 g/h and 811.6 g/h. Their titers,expressed as % by weight, are the following:

-   -   waste: carbon monoxide 45%, dimethyl ether 40%, others 5%;    -   crude MMA: MMA 61.8%, methanol 11.9%, water 22.3%, other light        compounds 0.5%, other heavy compounds 3.5% (i.e. an        esterification yield of 92.2 mol % expressed relative to the        inflowing methacrylamide);    -   “residual liquor”: ammonium hydrogen sulfate 58.5%, H₂SO₄ 13.8%,        H₂O 23.4%, unconverted methacrylamide 0.35%, MMA 0.37%,        methacrylic acid 0.43%, other compounds 3.15%.

The crude MMA is purified in the following way:

-   -   liquid-liquid extraction of the methanol with water;    -   topping of the light compounds by vacuum distillation;    -   topping of the heavy compounds by vacuum distillation.

These three operations are preferably carried out continuously and thefinal purity of the methyl methacrylate is greater than 99.5% by weight.

EXAMPLE 6 Mass Production of PMMA by a Continuous Process

A mixture containing 99.6% of methyl methacrylate of renewable originobtained in example 5, 0.38% of n-dodecyl mercaptan and 0.02% of DTAC(1,1-di(tert-amylperoxy)cyclohexane) is continuously introduced, at −40°C., into a stirred reactor kept at 160° C. and at a pressure of 10 bar.The reactor is emptied continuously at a mass flow rate that isidentical to the feed flow rate.

The heat generated by the polymerization reaction is thus consumed bythe introduction of the cold mixture and the emptying of the hotreaction mixture. For a reactor volume of one liter, a feed flow rate of21/h makes it possible to obtain a monomer conversion of approximately50 mol %. The reaction liquid constantly drawn off is then degassed soas to remove the excess methyl methacrylate in a continuously fedextruder provided with degassing wells. The polymer thus obtained at theoutlet of the extruder then contains 99.5% of PMMA and 0.5% of residualmonomer.

EXAMPLE 7 Manufacture of PMMA by the Cast Sheet Method

A mixture containing 99.943% of methyl methacrylate obtained in example5, 0.055% of azobisisobutyronitrile and 0.002% of terpinolene isdegassed in a vacuum flask at an absolute pressure of 500 mbar atambient temperature, kept under magnetic stirring for 20 minutes. Thisstep makes it possible to evacuate the gases dissolved in the mixture.The mixture thus degassed is then introduced into a mold consisting of 2glass plates of 10 mm separated by a PVC seal having a diameter of 4 mm,at ambient temperature. Pliers are used to obtain good leak-tightness ofthe whole. The mold is then slightly inclined and the air bubbles aredriven out by squeezing the PVC seal at the highest point of the mold.The whole is then introduced into a ventilated oven. Cooking is thencarried out at a temperature of 50° C. for 10 h, followed bypost-cooking at 130° C. for 30 minutes. After cooking, the whole iscooled to ambient temperature. A PMMA sheet is finally obtained bydismantling the mold. The PMMA sheet contains 99% of PMMA and 1% ofresidual monomer.

EXAMPLE 8 Manufacture of PMMA by the Suspension Process—Preparation of aSuspending Agent

120 parts of a solution of sodium hydroxide (NaOH) at 40% by weight and630 parts of deionized water are charged to a reactor provided withstirring. 250 parts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS)are slowly added to the reactor and then the pH is adjusted to between 7and 8 with a small amount of AMPS. After sufficient sparging of thesolution with nitrogen in order to remove oxygen, the reactor is heatedto 50° C. and then 0.075 part of potassium persulfate and 0.025 part ofsodium metabisulfite are added. The polymerization ends within 60minutes. The solution obtained is then diluted with 4000 parts ofdeionized water in order to obtain a solution which has a dry residue at160° C. of 5.5% by weight and a Brookfield viscosity of 4 Pa·s measuredat 25° C.

The suspension polymerization of methyl methacrylate and ethyl acrylateis carried out in the presence of the suspending agent as obtainedabove.

193 parts of deionized water and 7 parts of solution previously obtainedcorresponding to 0.385 part of dry product are charged to apressure-resistant stirred reactor. Oxygen is removed by sparging withnitrogen and the solution is heated to 80° C. 100 parts of adeoxygenated mixture composed of 96 parts of methyl methacrylateobtained, 4 parts of ethyl acrylate, 0.25 part oft-butylperoxy-2-ethylhexanoate and 0.25 part of butanethiol are thencharged to the reactor. The reactor is then hermetically sealed, and themixture is gradually heated to 110° C. over 120 minutes. The reactor isleft at 110° C. for a further 15 minutes and is then cooled.

The polymer, in the form of beads, is separated from the aqueoussolution by centrifugation, washed with deionized water and dried in anoven at 80° C.

EXAMPLE 9 Manufacture of an Impact Additive for PMMA

The following procedure is used to prepare an impact modifier havingseveral layers consisting of a hard core, an elastomeric soft layer anda hard crown.

The ratio of the three layers is 35/45/20 with each polymer having arefractive index of between 1.46 and 15.

The composition of the three layers is the following:

Layer 1: 74.8/25/0.2 MMA/EA/Alma Layer 2: 83.5/15.5/1 BA/STY/Alma Layer3: 95/5 MMA/EA With:

MMA: methyl methacrylateEA: ethyl acrylateBA: butyl acrylateSTY: styreneAlma: allyl methacrylate.

A monomer load consisting of 14% of layer 1 emulsified in water withpotassium dodecylbenzene sulfonate and potassium carbonate forcontrolling the pH is polymerized using potassium persulfate at 80° C.The remainder of the monomers of layer 1 (86%) are then added to thepreformed emulsion and then polymerized using potassium persulfate at80° C., while controlling the amount of surfactant added in order toavoid the formation of new particles.

Layer 2 is then added and polymerized using potassium persulfate at 80°C., while controlling the amount of surfactant added in order to avoidthe formation of new particles. Layer 3 is polymerized using potassiumpersulfate at 80° C., also while controlling the amount of surfactantadded in order to avoid the formation of new particles.

The latex obtained is then cooled and recovered by spray-drying. It canbe used to increase the impact strength of PMMA by mixing, for example,in an extruder.

1. A methyl methacrylate comprising from 0.2×10⁻¹⁰% to 1.2×10⁻¹⁰% bymass of ¹⁴C relative to the total mass of carbon according to standardASTM D6866.
 2. A monomer composition containing methyl methacrylate asdefined in claim 1, and at least one polymerizable comonomer.
 3. Thecomposition as claimed in claim 2, wherein the polymerizablecomonomer(s) is (are) chosen from vinyl, vinylidene, diene and olefinmonomers.
 4. A polymer composition comprising at least one polymerpolymerized from the methyl methacrylate as defined in claim
 1. 5. Thepolymer composition of claim 4, wherein said polymer is a homopolymer orcopolymer.
 6. The polymer composition of claim 5, wherein said polymeris a copolymer wherein said polymer composition has a random, block oralternating structure, or a core-shell structure.
 7. The polymercomposition of claim 6 wherein said copolymer is a block copolymer inwhich one of the blocks results from the polymerization of said methylmethacrylate.
 8. (canceled)
 9. The polymer composition as claimed inclaim 5, comprising: as a matrix polymer comprising at least one saidmethyl methacrylate homopolymer and/or at least one said copolymer; anda polymer additive chosen from block copolymers of said polymercomposition selected from the group consisting of the block copolymersmethyl (meth)acrylate-styrene, butyl (meth)acrylate-styrene,styrene-butadiene-methyl (meth)acrylate, and methyl (meth)acrylate-butylacrylate-methyl (meth)acrylate, and polymers having a core-shellstructure of said polymer composition.
 10. The polymer composition asclaimed in claim 9, wherein it said composition further comprises atleast one additive selected from the groups consisting of thermalstabilizers; lubricants; flame retardants; organic or inorganicpigments; anti-UV agents; antioxidants; antistatic agents; mattifyingagents, inorganic fillers and organic fillers.
 11. The polymercomposition as claimed in claim 9, wherein said composition is in theform of a powder, of granules or pellets.
 12. The polymer composition ofclaim 4, in the form of sheets, cast sheets, films, layers, fibers ortubes.
 13. The polymer composition of claim 4 in the form of amultilayer structure, wherein said multilayer structure comprises atleast one layer obtained from said polymer composition.
 14. The polymercomposition of claim 4 in the form of an extrudable resin, comprising: apolymer matrix comprising said polymer composition; and highlycrosslinked polymer particles.
 15. The polymer composition of claim 4 inthe form of a acrylic emulsion or resin.
 16. The polymer composition ofclaim 4 comprising a manufactured article selected from the groupconsisting of articles for the car industry, household articles, officearticles, signs and displays, transport articles, building articles,lighting articles, and bathroom articles.
 17. The polymer composition ofclaim 16 wherein said article is obtained by extrusion, coextrusion, hotpressing or multi-injection molding.
 18. A method for the manufacturemethyl methacrylate as defined in claim 1, comprising the steps of a)condensing of hydrocyanic acid with acetone to form acetone cyanohydrin,and, b) introducing methanol to form methyl methacrylate, characterizedin that at least one from acetone, hydrocyanic acid and methanol wasobtained by a reaction or a succession of reactions starting frombiomass.
 19. The method as claimed in claim 18, wherein the acetone isobtained by acetobutylic fermentation of C₆ and C₅ sugars, resulting inan acetone-butanol mixture, where appropriate with ethanol, from whichthe acetone was separated by distillation or by membrane separation orby separation on silicalite, or other means of separation.
 20. Themethod as claimed in claim 18, wherein the acetone is obtained byhydrothermal liquefaction at 573 K of sewage treatment sludge so as toobtain black water containing hydrocarbons, followed by catalyticcracking of said black water in a steam atmosphere on a catalyst basedon zirconia or zirconia/alumina supported on iron oxide, and thenseparation of the acetone, by distillation, or by membrane separation orseparation on silicalite, or other means of separation.
 21. The methodas claimed in claim 18, wherein the acetone is obtained by catalyticconversion of palm oil residues on a catalyst of zirconia orzirconia/alumina supported on iron oxide, and then separation of theacetone, by distillation, or by membrane separation or separation onsilicalite, or other means of separation.
 22. The method as claimed inclaim 18, wherein the hydrocyanic acid is obtained by ammoxidation ofmethane, the methane having been obtained by fermentation, in theabsence of oxygen, of animal and/or plant organic materials, resultingin a biogas mainly composed of methane and carbon dioxide, the carbondioxide having been removed by washing the biogas with a basic aqueoussolution of sodium hydroxide, potassium hydroxide or amine, or else withwater under pressure, or by absorption in a solvent.
 23. The method asclaimed in claim 18, wherein the hydrocyanic acid is obtained byammoxidation of methanol, the methanol having been obtained by pyrolysisof wood or by gasification of any materials of animal and/or plantorigin, resulting in a syngas mainly composed of carbon monoxide andhydrogen which is reacted with water, or by fermentation starting fromplant crops giving fermentable products and therefore alcohol.
 24. Themethod as claimed in claim 18, wherein the methanol is obtained bypyrolysis of wood or by gasification of any materials of animal or plantorigin, resulting in a syngas mainly composed of carbon monoxide andhydrogen which is reacted with water, or by fermentation starting fromplant crops giving fermentable products and therefore alcohol.
 25. Themethod as claimed in claim 23, wherein the syngas for preparing themethanol is obtained from the residual liquor from the manufacture andbleaching of cellulosic pulps.
 26. The method as claimed in claim 18,wherein: in a first step, hydrocyanic acid is condensed with acetone viaa basic catalysis in order to obtain acetone cyanohydrin; in a secondstep, the acetone cyanohydrins is reacted in a concentrated sulfuricmedium in order to obtain α-oxyisobutyramide monosulfate, which isconverted to sulfuric methacrylamide under the action of the heat of thereaction which is highly exothermic; in a third step, the methacrylamideis hydrolyzed and esterified with methanol so as to form methylmethacrylate and ammonium hydrogen sulfate, and the desired startingmaterial is recovered.
 27. The method as claimed in claim 18, wherein:in a first step, hydrocyanic acid is condensed with acetone via a basiccatalysis in order to obtain acetone cyanohydrin; in a second step, theacetone cyanohydrin is reacted with methanol in order to obtain methylhydroxymethacrylate; in a third step, the methyl hydroxymethacrylate isdehydrated so as to recover the desired starting material. 28.(canceled)
 29. The method as claimed in claim 24, wherein the syngas forpreparing the methanol is obtained from the residual liquor from themanufacture and bleaching of cellulosic pulps.